CN111331708A - Water-soluble die material for resin-based composite material - Google Patents

Water-soluble die material for resin-based composite material Download PDF

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Publication number
CN111331708A
CN111331708A CN202010150405.9A CN202010150405A CN111331708A CN 111331708 A CN111331708 A CN 111331708A CN 202010150405 A CN202010150405 A CN 202010150405A CN 111331708 A CN111331708 A CN 111331708A
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water
soluble
mould
filler
mold
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CN111331708B (en
Inventor
李晓丹
隋岩
王冠辉
肖�琳
刘诚
王玮
丁超
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Jinggangshan University
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Jinggangshan University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B3/00Producing shaped articles from the material by using presses; Presses specially adapted therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/04Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/24Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
    • B28B11/243Setting, e.g. drying, dehydrating or firing ceramic articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00Moulds or cores; Details thereof or accessories therefor
    • B29C33/38Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3842Manufacturing moulds, e.g. shaping the mould surface by machining
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/30Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Other silicon-containing organic compounds; Boron-organic compounds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/30Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Other silicon-containing organic compounds; Boron-organic compounds
    • C04B26/32Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Other silicon-containing organic compounds; Boron-organic compounds containing silicon
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61Coating or impregnation
    • C04B41/62Coating or impregnation with organic materials
    • C04B41/64Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention relates to a method for preparing a water-soluble mould material for a resin-based composite material, which belongs to the field of new materials and consists of a water-soluble ceramic precursor aqueous solution and a filler for a water-soluble mould, wherein the mass percentage concentration of the water-soluble ceramic precursor aqueous solution is 10-30%, and the solute mass of the ceramic precursor aqueous solution is 1-15% of the mass of the filler for the water-soluble mould.

Description

Water-soluble die material for resin-based composite material
Technical Field
The invention relates to a method for manufacturing a water-soluble die material for a resin-based composite material, belonging to the field of new materials.
Background
The adhesive used in the traditional water-soluble material comprises inorganic salt and water-soluble polymer, and the salt core (core mold) made of the material has strong hygroscopicity, poor surface quality of the core and difficult guarantee of dimensional accuracy. The water-soluble polymer is a high molecular compound with hydrophilic groups, the frequently used water-soluble mould material of the resin-based composite material is polyvinyl alcohol, although the forming is easy, the glass transition temperature is low, the thermal stability is poor, and the polyvinyl alcohol has the phenomena of blackening, sintering and the like when the curing temperature exceeds 150 ℃, so that the mould material is difficult to completely clean when demoulding. For the molding process of composite materials with higher curing temperature, water-soluble materials like polyvinyl alcohol can not meet the use requirements, and a water-soluble polymer with higher temperature resistance is needed. With the continuous emergence of high temperature resistant and ablation resistant resin, the curing temperature is increased, which reaches 375 ℃ at most, and the prior art does not provide a high temperature resistant (over 375 ℃) water-soluble mold (core mold) material for resin-based composite materials and a method for manufacturing the water-soluble mold until now.
Disclosure of Invention
The invention aims to provide a water-soluble mould material for a resin-based composite material and a method for manufacturing the water-soluble mould, which aim to solve the problem of poor high-temperature resistance of the existing water-soluble mould (core mould) for the resin-based composite material.
The technical scheme adopted by the invention for solving the technical problems is as follows:
resin matrixThe water-soluble mold material for the composite material consists of a water-soluble ceramic precursor aqueous solution and a water-soluble mold filler; the mass percentage concentration of the water-soluble ceramic precursor aqueous solution is 10-30%; the structure of the ceramic precursor is
Figure BDA0002402243160000021
The structure is that the main chain is-O-A-O-, A is one of silicon and titanium, and can form A ceramic material precursor which is compounded by organic silicon and titanate through covalent bonds with oxygen, and the side chain B is grafted with A water-soluble substituent which is one of hydroxyl, carboxyl, amido and amido compounds or polymers thereof; the solute mass of the ceramic precursor water solution is 1-15% of the mass of the water-soluble mold filler; the water-soluble mold filler is one or a mixture of micron-sized silicon dioxide, micron-sized aluminum oxide and micron-sized titanium dioxide hollow ceramic microspheres.
Preferably, the water-soluble mould material also comprises an auxiliary filler for the water-soluble mould, and the mass of the auxiliary filler is 1-10% of that of the filler for the water-soluble mould; the auxiliary filler for the water-soluble die is micron-sized graphite powder or micron-sized metal powder.
The mold comprises the following steps:
(1) preparing materials: dissolving a ceramic precursor in water to prepare a water solution with the concentration of 10-30%, adding a water-soluble mold filler, wherein the mass of the water-soluble ceramic precursor is 1-15% of that of the water-soluble mold filler, and uniformly stirring to prepare a water-soluble mold material;
(2) preforming: putting the water-soluble mould material prepared in the step (1) into a mould for manufacturing a water-soluble mould or a core mould, and compacting to prepare the required shape of the water-soluble mould;
(3) and (3) drying: drying the preformed water-soluble mould prepared in the step (2) at the drying temperature of 100-200 ℃ until the preformed water-soluble mould is dried to prepare a formed water-soluble mould;
(4) and (3) machining: machining the surface of the dried preformed water-soluble mould to obtain a water-soluble mould with the geometric dimension precision of 0.01 mm;
(5) surface treatment: coating a ceramic precursor aqueous solution with the mass percentage concentration of 10-30% on the outer surface of the water-soluble mould after mechanical processing, and drying, wherein the dried coating forms a hard protective film on the outer surface of the water-soluble mould; and preparing the water-soluble mold.
Preferably, the method for manufacturing the water-soluble mold comprises the following steps: in the step (3), the drying temperature is 150 ℃.
Preferably, the method for manufacturing the water-soluble mold comprises the following steps: in the step (5), the mass percentage concentration of the water-soluble ceramic precursor aqueous solution is 15%.
The invention has the advantages that
(1) The water-soluble ceramic precursor adopted by the water-soluble mould material prepared by the invention is a substance with good thermal stability, can be dissolved when being heated to 800 ℃, has good high-temperature resistance, and is suitable for forming resin-based composite materials with high curing temperature.
(2) The adopted filler is inorganic filler, the core die prepared by the inorganic filler has light weight, small thermal expansion coefficient and appearance and size which can be machined according to requirements, the water-soluble die material containing the water-soluble ceramic precursor has certain mechanical strength, the compression strength of a cube with the side length of 25.4mm is tested, the compression strength reaches 8MPa or above, and the retention rate at 300 ℃ is still high.
(3) Compared with the traditional casting type water-soluble mould material added with gypsum powder, the casting type water-soluble mould material has the advantage that the compression strength of the water-soluble mould can be controlled by changing the preforming pressure under the condition of keeping the formula ratio unchanged.
Drawings
Fig. 1 is a flow chart of the process of making the water-soluble mold according to the present invention (steps one to five).
Detailed Description
Example 1
The preparation method of the mould comprises the following steps:
preparing materials: dissolving a ceramic precursor with an organic silicon structure as a main chain in water to prepare a 20% aqueous solution, adding a water-soluble mold filler, and uniformly stirring to prepare a water-soluble mold material, wherein the mass of the water-soluble ceramic precursor is 8% of that of the water-soluble mold filler;
the filler is: ordinary sand
Preforming: putting the water-soluble mould material prepared in the step (1) into a mould for manufacturing a water-soluble mould or a core mould, and compacting to prepare the required shape of the water-soluble mould;
and (3) drying: drying the preformed water-soluble mould prepared in the step (2) at the drying temperature of 150 ℃ until the preformed water-soluble mould is dried to prepare a formed water-soluble mould; and (3) machining: machining the surface of the dried preformed water-soluble mould to obtain a water-soluble mould;
surface treatment: coating a ceramic precursor aqueous solution with the mass percentage concentration of 20% on the outer surface of the water-soluble mould after mechanical processing, and drying, wherein the dried coating forms a hard protective film on the outer surface of the water-soluble mould; and preparing the water-soluble mold.
In the step (3), the drying treatment temperature is 150 ℃.
In the step (5), the mass percentage concentration of the water-soluble ceramic precursor aqueous solution is 15%.
Example 2
The filler for the water-soluble mold in the embodiment is one or a mixture of micron-sized silicon dioxide, micron-sized aluminum oxide and micron-sized titanium dioxide hollow ceramic microspheres. The other components are the same as those in the first embodiment.
Example 3
The filler for the water-soluble mold is formed by uniformly mixing any two or more than two of micron-sized silicon dioxide, micron-sized aluminum oxide and micron-sized titanium dioxide hollow ceramic microspheres according to any ratio.
Example 4
The water-soluble high molecular polymer aqueous solution according to the present embodiment is an aqueous solution of a water-soluble ceramic precursor having a main chain of an organic silicon structure at a concentration of 25% by mass, and the rest is the same as in example 1.
Example 5
In the present embodiment, the mass of the solute in the aqueous solution of the water-soluble ceramic precursor having the main chain of the organosilicon structure is 10% of the mass of the filler for the water-soluble mold. The rest is the same as example 1.
Example 6
The water-soluble mold material of the embodiment further comprises an auxiliary filler for the water-soluble mold, wherein the mass of the auxiliary filler for the water-soluble mold is 25% of that of the filler for the water-soluble mold; the auxiliary filler for the water-soluble die is micron-sized graphite powder. The rest is the same as example 1.
Example 7
Referring to fig. 1, the method for manufacturing a water-soluble mold according to the present embodiment is implemented as follows:
step one, batching: dissolving a water-soluble ceramic precursor with a main chain of-O-Ti-O-structure in water to prepare a water solution with the concentration of 10%, adding a water-soluble mold filler after the water-soluble ceramic precursor is completely dissolved, wherein the mass of the water-soluble ceramic precursor water solution is 15% of that of the water-soluble mold filler, and uniformly stirring to prepare a water-soluble mold material;
step two, preforming: putting the water-soluble mould material prepared in the step one into a mould for preparing a water-soluble mould or a core mould, and compacting to prepare the required shape of the water-soluble mould (the core mould), so that the workload of machining can be reduced; or the water-soluble mould material prepared in the step one is made into a preformed block, and the required shape of the water-soluble mould (core mould) is prepared by various machining means; in the preforming process, the larger the pressure applied to the die material is, the stronger the pressure resistance of the manufactured core die is;
step three, drying: drying the preformed water-soluble mould prepared in the third step at the drying temperature of 100 ℃ until the preformed water-soluble mould is dried to prepare a formed water-soluble mould; the drying time depends on the size of the sample to be dried, and the larger the size of the sample, the longer the drying time is needed; during drying, the preformed core mold can be placed into a drying oven for drying; the moisture in the composite must be completely dried out by drying, otherwise the performance of the composite is affected;
step four, machining: machining the surface of the pre-formed water-soluble mould after drying to obtain a water-soluble mould (core mould) with a precise geometric dimension; the pre-forming block can be processed by various machining means, and can be processed into various required shapes including various arcs; during machining, the direction of the cutter entering is taken into consideration, so that defects at edges and corners are avoided;
step five, surface treatment: coating a layer of water-soluble ceramic precursor water solution with the mass percentage concentration of 20% on the outer surface of the water-soluble mould (core mould) after machining, and drying, wherein the dried coating forms a hard protective film on the outer surface of the water-soluble mould (core mould); the desired water-soluble mold (mandrel) is produced.
The purpose of surface treatment after the mandrel is processed into a required shape is as follows: so as to avoid the problem that glue (the glue on the prepreg for composite material molding) seeps into tiny gaps of the water-soluble core mold material in the curing process and brings difficulty to the removal of the core mold material.
The water-soluble molds obtained in examples 1 to 7 were tested, heated to 500 deg.C, 600 deg.C, and 800 deg.C, respectively, and the dissolved state thereof was recorded, and the specific results are shown in Table 1, and the molds of examples 1 to 7 were tested for their compressive strength using a cube having a side length of 25.4mm, and the strength retention rates at 100 deg.C, 200 deg.C, and 300 deg.C were recorded, and the results are shown in Table 2.
TABLE 1
Figure BDA0002402243160000071
Figure BDA0002402243160000081
TABLE 2
Figure BDA0002402243160000082

Claims (7)

1. A water-soluble mould material for resin-based composite materials is characterized in that: consists of water-soluble ceramic precursor water solution and water-soluble mold filler; the mass percentage concentration of the water-soluble ceramic precursor aqueous solution is 10-30%; the structure of the ceramic precursor is
Figure FDA0002402243150000011
The structure is that the main chain is-O-A-O-, A is one of silicon and titanium, and can form A ceramic material precursor which is compounded by organic silicon and titanate through covalent bonds with oxygen, and the side chain B is grafted with A water-soluble substituent which is one of hydroxyl, carboxyl, amido and amido compounds or polymers thereof; the solute mass of the ceramic precursor water solution is 1-15% of the mass of the water-soluble mold filler; the water-soluble mold filler is one or a mixture of micron-sized silicon dioxide, micron-sized aluminum oxide and micron-sized titanium dioxide hollow ceramic microspheres.
2. The water-soluble mold material for resin-based composite materials according to claim 1, characterized in that: the water-soluble ceramic precursor water solution is a ceramic precursor water solution with the mass percentage concentration of 15%.
3. The water-soluble mold material for resin-based composite materials according to claim 1, characterized in that: the mass of the water-soluble ceramic precursor solute is 10% of the mass of the filler for the water-soluble mold.
4. The water-soluble mold material according to any one of claims 1 to 3, wherein: the water-soluble mould material also comprises an auxiliary filler for the water-soluble mould, and the mass of the auxiliary filler is 1-10% of that of the filler for the water-soluble mould; the auxiliary filler for the water-soluble die is micron-sized graphite powder or micron-sized metal powder.
5. A method of making a mould using the water soluble mould material according to any one of claims 1 to 3, characterised in that it consists of the steps of:
(1) preparing materials: dissolving a ceramic precursor in water to prepare a water solution with the concentration of 10-30%, adding a water-soluble mold filler, wherein the mass of the water-soluble ceramic precursor is 1-15% of that of the water-soluble mold filler, and uniformly stirring to prepare a water-soluble mold material;
(2) preforming: putting the water-soluble mould material prepared in the step (1) into a mould for manufacturing a water-soluble mould or a core mould, and compacting to prepare the required shape of the water-soluble mould;
(3) and (3) drying: drying the preformed water-soluble mould prepared in the step (2) at the drying temperature of 100-200 ℃ until the preformed water-soluble mould is dried to prepare a formed water-soluble mould;
(4) and (3) machining: machining the surface of the dried preformed water-soluble mould to obtain a water-soluble mould with the geometric dimension precision of 0.01 mm;
(5) surface treatment: coating a ceramic precursor aqueous solution with the mass percentage concentration of 10-30% on the outer surface of the water-soluble mould after mechanical processing, and drying, wherein the dried coating forms a hard protective film on the outer surface of the water-soluble mould; and preparing the water-soluble mold.
6. The method of making a water soluble mold as recited in claim 5, wherein: in the step (3), the drying temperature is 150 ℃.
7. The method of making a water soluble mold as recited in claim 5, wherein: in the step (5), the mass percentage concentration of the water-soluble ceramic precursor aqueous solution is 15%.
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CN108439998A (en) * 2018-03-06 2018-08-24 济南大学 A kind of preparation method of gel casting forming titanium nitride ceramic biscuit
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CN101665609A (en) * 2009-10-29 2010-03-10 哈尔滨玻璃钢研究院 Water-soluble die material for resin matrix composite materials and method for manufacturing water-soluble die
US20190189892A1 (en) * 2017-12-14 2019-06-20 Eastman Kodak Company Composite article with co-planar electrodes
CN108439998A (en) * 2018-03-06 2018-08-24 济南大学 A kind of preparation method of gel casting forming titanium nitride ceramic biscuit
CN109020593A (en) * 2018-09-08 2018-12-18 佛山皖和新能源科技有限公司 A kind of elasticity refractory ceramics thermal insulation tile and preparation method thereof

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